Bis-substituted succinamides and their utility as herbicides

ABSTRACT

Bis-substituted succinamides having the formula ##STR1## in which X is chlorine or bromine; R 1  and R 3  are each hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, or benzyl; R 2  and R 4  are each hydrogen, alkyl, alkenyl, haloalkenyl, alkoxyalkyl, alkynyl, cycloalkyl, cyclopropylmethyl, furfuryl, and tetrahydrofurfuryl; R 1  and R 2  taken together along with the nitrogen form a non-aromatic heterocyclic ring; R 3  and R 4  taken together along with the nitrogen form a non-aromatic heterocyclic ring; provided that when R 1 , R 2 , R 3  and R 4  are each alkyl, then one of R 1  or R 2  and one of R 3  or R 4  is other than methyl; further provided that only one of R 1  or R 2  is hydrogen and only one of R 3  or R 4  is hydrogen. Compounds of this invention are useful as herbicides and includes those compounds in which R 1 , R 2 , R 3  and R 4  are each methyl.

This is a continuation, of application Ser. No. 960,379, filed Nov. 13, 1978 now abandoned, which in turn is a division of application Ser. No. 821,688, filed Aug. 4, l977, now U.S. Pat. No. 4,143,070 issued Mar. 6, l979, which in turn is a division of application Ser. No. 546,234, filed Feb. 3, 1975, now U.S. Pat. No. 4,056,524, which is a continuation-in-part of application Ser. No. 459,438, filed Apr. 9, 1974, now abandoned which is a continuation-in-part of Ser. No. 410,641, filed Nov. 12, 1973, now abandoned.

This invention relates to certain novel bis-substituted succinamides which can be used as herbicides. More specifically, this invention relates to certain α-halo bis-substituted succinamides, to their preparation and utility of the compounds as herbicides.

The compounds comprising the instant class of compounds correspond to the general formula: ##STR2## in which X is chlorine or bromine; R₁ and R₃ are each hydrogen, alkyl having from 1 to 8 carbon atoms, inclusive, haloalkyl having from 1 to 6 carbon atoms, inclusive, in which halo is fluorine, bromine and chlorine, alkenyl having from 2 to 6 carbon atoms, inclusive, alkynyl having from 2 to 8 carbon atoms, inclusive, or benzyl; R₂ and R₄ are each hydrogen, alkyl having from 1 to 8 carbon atoms, inclusive, alkenyl having from 2 to 6 carbon atoms, inclusive, haloalkenyl having from 2 to 6 carbon atoms, inclusive, in which halo is chlorine or bromine, alkoxyalkyl having from 2 to 8 carbon atoms, inclusive, alkynyl having from 2 to 6 carbon atoms, inclusive, cycloalkyl having from 3 to 7 carbon atoms, inclusive, cyclopropylmethyl, furfuryl, and tetrahydrofurfuryl; R₁ and R₂ taken together along with the nitrogen form a non-aromatic heterocyclic ring having from 2 to 8 carbon atoms, inclusive; R₃ and R₄ taken together along with the nitrogen form a non-aromatic heterocyclic ring having from 2 to 8 carbon atoms, inclusive; provided that when R₁, R₂, R₃ and R₄ are each alkyl, then one of R₁ or R₂ and one of R₃ or R₄ is other than methyl; further provided that only one of R₁ or R₂ is hydrogen and only one of R₃ or R₄ is hydrogen.

In the above description, the following preferred embodiments are intended for the various substituent groups: Alkyl and haloalkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branch chain configurations, for example, methyl, trifluoromethyl, ethyl, 2-chloroethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, n-hexyl, isohexyl, octyl, isooctyl and the like; alkenyl preferably includes, unless otherwise provided for, those members which contain at least one olefinic double bond and containing from 2 to 6 carbon atoms, inclusive, for example, allyl, methallyl, ethallyl, 1-butenyl, 3-butenyl, 2-methyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-methyl-1-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and the like; alkenyl and haloalkenyl preferably includes, unless otherwise specified for, those members which contain from 2 to 6 carbon atoms, inclusive, and halo preferably includes chloro or bromo; and alkynyl preferably includes those members which contain from 2 to 8 carbon atoms, inclusive, and at least one acetylenic unsaturation (triple bond), for example, 1-propynyl, 2-propynyl (propargyl), 2-butenyl, 3-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 1-ethynylcyclohexyl and the like; alkoxyalkyl preferably includes those members which contain a total of from 2 to 8 carbon atoms, inclusive, for example, methoxymethyl, methoxyethyl, methoxypropyl, ethoxyethyl, propoxymethyl, propoxypropyl, methoxybutyl and the like; cycloalkyl preferably includes, unless otherwise provided for, those members which contain from 3 to 7 carbon atoms, inclusive, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like; R₁ and R₂ taken together along with the nitrogen, and R₃ and R₄ taken together along with the nitrogen, form non-aromatic heterocyclic ring, preferably includes, unless otherwise provided for, those members which contain from 2 to 6 carbon atoms, inclusive, for example, including those divalent radicals derived from normal alkanes or alkenes by removal of a hydrogen atom from each of the two terminal carbon atoms of the chain, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, butene-2 and pentene-2; also included are those branch chain members wherein said branched member is a lower alkyl of from 1 to 4 carbon atoms, including such as ethylethylene, methylpentamethylene, 3-methylpentamethylene and the like, and with another hetero-atoms, such as nitrogen or oxygen radicals such as in β-oxydiethylene and β-iminodiethylene,

The compounds of this invention have been found to be active herbicides of a general type. Included in the compounds active as herbicides and therefore useful in the method of controlling undesirable vegetation, are those compounds in which R₁, R₂, R₃ and R₄ are each methyl. That is, certain members of the class have been found to be herbicidally effective against a wide range of plant species. A method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area of plant locus where control is desired.

An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By a "growth controlling amount" is meant an amount of compound which causes a modifying effect upon the growth of plants. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoilation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants", it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The intermediate α-halosuccinoyl chlorides are prepared from the α-halosuccinic acid and phosphorus pentachloride according to the procedure of Freudenberg and Lux, Ber. 61B, pp. 1083-9 at p. 1087 (1928). This reference also discloses the compound bromosuccinic acid-bis-dimethyl amide. According to the procedure by Walden, Ber. 26, p. 214 (1893) hydroxy succinic acid (malic acid) can be reacted with phosphorus pentachloride to prepare the corresponding diacid chlorides.

The bis-substituted succinamides are prepared by several different methods, depending upon the nature of the starting materials and products desired. A preferred method, for example, is the reaction of a desired primary or secondary amine with the α-halosuccinoyl chloride in a suitable solvent such as benzene, methylene, chloride, diethyl ether and the like. The use of a solvent is useful to facilitate processing of the reaction and to aid in the agitation by providing adequate volume, as well as solubilizing the reagents. The preferred ratio of amine to acid chloride is 4 to 1. When the amine is used in excess as preferred, the amine acts as an acid acceptor in the reaction. Other amines, at tertiary amines, can be employed as acid acceptors when the ratio of reactant amine to α-halosuccinoyl chloride is 2 to 1. The addition of reagents in the reaction preferably is such that permits the amine to be added to the α-halosuccinoyl chloride in solution. The temperatures for the reaction are best defined between about -30° C. and about +10° C. At these temperatures, the reaction as described hereinabove proceeds rapidly to yield the desired product. In each instance after the reaction is complete, the recovery is carried out by normal work-up procedures, such as crystallization, sublimation or distillation.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples is a table of compounds which are prepared according to the procedures described herein.

EXAMPLE I Preparation of Bis-N,N-diallyl-α-bromosuccinamide

A solution of 11.7 g. diallylamine (0.12 mole) in 25 ml. methylene chloride (0.03 mole) in 75 ml. methylene chloride at -30° to -25° C. The reaction mixture was stirred for 1/2 hour after amine addition was complete during which time the temperature rose to 10° C.

The product was stirred with 100 ml. water, phase separated and then washed with two 100 ml. portions of 5% sulfuric acid solution and one 100 ml. portion of 5% sodium bicarbonate solution. The organic solution was dried over magnesium sulfate, filtered, and the solvent evaporated under vacuum. There was obtained 8.1 g. of the title compound N_(D) ³⁰ =1.5196.

EXAMPLE II Preparation of N,N'-dibenzyl-α-bromosuccinamide

A solution of 7.3 g. benzylamine (0.068 mole) and 8.2 g. N,N-dimethylaniline (0.068 mole) in 25 ml. methylene chloride was added dropwise with stirring to 8.0 g. α-bromosuccinoyl chloride (0.034 mole) in 75 ml. methylene chloride at -30° C. to -25° C. The reaction mixture was washed with 100 ml. water. The insoluble solid was removed by filtration and air-dried to give 2.9 g. of the title compound, m.p. 232° C. (dec.). Identification was confirmed by n.m.r. analysis.

EXAMPLE III Preparation of N,N'-dipiperidino-α-chlorosuccinamide (1,1'-dichlorosuccinoyl dipiperidine)

A solution of 8.9 g. piperidine (0.104 mole) in 25 ml. methylene chloride was added dropwise with stirring to a solution of 5.0 g. (0.026 mole) α-chlorosuccinoyl chloride in 75 ml. methylene chloride at -30° to -25° C. The reaction mixture was stirred for 1/2 hour after addition was complete, during which time the temperature rose to 12° C.

The mixture was next stirred with 100 ml. of water, phase separated and the organic layer was washed successively with two 100 ml. portions of dilute hydrochloric acid and two 100 ml. portions of water.

After drying over magnesium sulfate, the solvent was removed in vacuum to leave an oil, 6.5 g., N_(D) ³⁰ =1.5111, identified by n.m.r. analysis to be the title compound.

EXAMPLE IV Preparation of Bis-N,N-diethyl-α-bromosuccinamide

A solution of 6.9 g. diethylamine (0.09 mole) in 75 ml. toluene and 6.4 g. 50% aqueous sodium hydroxide (0.08 mole) diluted with 10 ml. water were mixed and cooled to -15° C. A solution of 10.0 g. α-bromosuccinoyl chloride (0.04 mole) in 10 ml. toluene was added dropwise to the mixture with rapid stirring at -15° to -10° C. The reaction mixture was stirred for 1/2 hour after addition was complete, during which time the temperature rose to 15° C.

The mixture was phase separated and the organic layer was washed successively with 100 ml. water, two 100 ml. portions of dilute hydrochloric acid and two 100 ml. portions of water.

After drying over magnesium sulfate, the solvent was removed in vacuum. There was obtained an oil, 8.9 g., N_(D) ³⁰ =1.4955, identified by n.m.r. analysis to be the title compound.

The following is a table of compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

                                      TABLE I                                      __________________________________________________________________________      ##STR3##                                                                      COM-                                                                           POUND                                                  m.p. °C.         NUMBER X R.sub.1  R.sub.2       R.sub.3  R.sub.4       or                      __________________________________________________________________________                                                            N.sub.D.sup.30          1      Br                                                                               H        (CH.sub.3).sub.3 C                                                                           H        (CH.sub.3).sub.3 C                                                                           179°                                                                    (dec.)                  2      Br                                                                               CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                                                           CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                                                           1.5196                  3      Br                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CClCH.sub.2                                                                          CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CClCH.sub.2                                                                          1.5154                  4      Br                                                                               φCH.sub.2                                                                           H             φCH.sub.2                                                                           H             232°                                                                    (dec.)                  5      Br                                                                               CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          1.5355                  6      Cl                                                                               CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          1.521                   7      Br                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                                   CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                                   1.4863                  8      Br                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CHCH.sub.2                                                                           CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CHCH.sub.2                                                                           1.5046                  9      Br                                                                               CH.sub.3 O(CH.sub.2).sub.3                                                              H             CH.sub.3 O(CH.sub.2).sub.3                                                              H             107-110                 10     Cl                                                                               CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                                                           CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                                                           1.5082                  11     Cl                                                                               (CH.sub.2).sub.5       (CH.sub.2).sub.5       1.5111                  12     Br                                                                               CH.sub.3 CHCCH(CH.sub.3)                                                                              CH.sub.3 CHCCH(CH.sub.3)                                                                              1.5178                  13     Br                                                                               C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                              1.4955                  14     Cl                                                                               CH.sub.3 C.sub.2 H.sub.5                                                                              CH.sub.3 C.sub.2 H.sub.5                       15     Br                                                                                ##STR4##                                                                                              ##STR5##              dark solid              16     Br                                                                                ##STR6##                                                                               CH.sub.3                                                                                      ##STR7##                                                                               CH.sub.3      1.5651                  17     Cl                                                                               (CH.sub.2).sub.4       (CH.sub.2).sub.4       64-68                   18     Br                                                                               CH.sub.2CHCH.sub.2                                                                       ##STR8##     CH.sub.2CHCH.sub.2                                                                       ##STR9##     1.5250                  19     Br                                                                               CH.sub.3                                                                                 ##STR10##    CH.sub.3                                                                                 ##STR11##    1.5238                  20     Br                                                                               CH.sub.3 CH.sub.2                                                                       CH.sub.2CHCH.sub.2                                                                           CH.sub.3 CH.sub.2                                                                       CH.sub.2CHCH.sub.2                                                                           1.5095                  21     Br                                                                               CH.sub.3 CH.sub.2CHCH.sub.2                                                                           CH.sub.3 CH.sub.2CHCH.sub.2                                                                           1.5178                  22     Br                                                                               (CH.sub.2).sub.5       (CH.sub.2).sub.5       1.5296                  23     Br                                                                                n-C.sub.4 H.sub.9                                                                      CH.sub.2CHCH.sub.2                                                                           n-C.sub.4 H.sub.9                                                                       CH.sub.2CHCH.sub.2                                                                           1.4984                  24     Br                                                                                ##STR12##                                                                              CH.sub.2CHCH.sub.2                                                                            ##STR13##                                                                              CH.sub.2CHCH.sub.2                                                                           1.4969                  25     Br                                                                               HCCCH.sub.2                                                                             HCCCH.sub.2   HCCCH.sub.2                                                                             HCCCH.sub.2   1.5323                  26     Cl                                                                               HCCCH.sub.2                                                                             HCCCH.sub.2   HCCCH.sub.2                                                                             HCCCH.sub.2                           27     Br                                                                               CH.sub.3                                                                                 ##STR14##    CH.sub.3                                                                                 ##STR15##    1.5156                  28     Cl                                                                               CH.sub.3                                                                                 ##STR16##    CH.sub.3                                                                                 ##STR17##                            29     Br                                                                               BrCH.sub.2 CH.sub.2 CH.sub.2                                                            H             BrCH.sub.2 CH.sub.2 CH.sub.2                                                            H             106°                                                                    (dec.)                  30     Cl                                                                               BrCH.sub.2 CH.sub.2 CH.sub.2                                                            H             BrCH.sub.2 CH.sub.2 CH.sub.2                                                            H                                     31     Br                                                                               H        CHCC(CH.sub.3).sub.2                                                                         H        CHCC(CH.sub.3).sub.2                                                                         123°                                                                    (dec.)                  32     Br                                                                               (CH.sub.2).sub.6       (CH.sub.2).sub.6       1.5322                  33     Br                                                                               H        CH.sub.2 CH.sub.2 CH.sub.3                                                                   H        CH.sub.2 CH.sub.2 CH.sub.3                                                                   155-157°         34     Cl                                                                               H        CH.sub.2 CHCH.sub.2                                                                          H        CH.sub.2 CHCH.sub.2                                                                          170-171°         35     Br                                                                               H        HCCCH.sub.2   H        HCCCH.sub.2   148-149°         36     Br                                                                               H        CH.sub.3 (CH.sub.2).sub. 4                                                                   H        CH.sub.3 (CH.sub.2).sub.4                                                                    140-143°         37     Br                                                                               H                                                                                        ##STR18##    H                                                                                        ##STR19##    186°                                                                    (dec.)                  38     Cl                                                                                ##STR20##                                                                                             ##STR21##             72-79°           39     Br                                                                                ##STR22##                                                                                             ##STR23##             79-82°           40     Br                                                                               H        CH.sub.3 CHCHCH.sub.2                                                                        H        CH.sub.3 CHCHCH.sub.2                                                                        166-167°         41     Br                                                                               H                                                                                        ##STR24##    H                                                                                        ##STR25##    161°                                                                    (dec.)                  42     Br                                                                               H        CH.sub.2C(CH.sub.3)CH.sub.2                                                                  H        CH.sub.2C(CH.sub.3)CH.sub.2                                                                  145°                                                                    (dec.)                  43     Br                                                                               H        (CH.sub.3).sub.2 CH(CH.sub.2).sub.2                                                          H        (CH.sub.3).sub.2 CH(CH.sub.2).sub                                              .2            122-126°         44     Cl                                                                                ##STR26##                                                                                             ##STR27##             1.5098                  45     Cl                                                                                ##STR28##                                                                                             ##STR29##             1.5052                  46     Br                                                                               BrCH.sub.2 CH.sub.2                                                                     H             BrCH.sub.2 CH.sub.2                                                                     H             156°                                                                    (dec.)                  47     Cl                                                                                ##STR30##                                                                                             ##STR31##             102-104°         48     Br                                                                               H        CH.sub.2CClCH.sub.2                                                                          H        CH.sub.2CClCH.sub.2                                                                          166-167°                                                                (dec.)                  49     Br                                                                               H        CH.sub.3      H        CH.sub.3      153-155°         50     Br                                                                               H        CH.sub.2 CH.sub.3                                                                            H        CH.sub.2 CH.sub.3                                                                            180-181°         51     Br                                                                               H        (CH.sub.3).sub.2 CH                                                                          H        (CH.sub.3).sub.2 CH                                                                          169°                                                                    (dec.)                  52     Br                                                                               H        CH.sub.3 (CH.sub.2).sub.3                                                                    H        CH.sub.3 (CH.sub.2).sub.3                                                                    141-142°         53     Br                                                                               H        (CH.sub.3).sub.2 CHCH.sub.2                                                                  H        (CH.sub.3).sub.2 CHCH.sub.2                                                                  141-142°         54     Br                                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)                                                               158-161°         55     Br                                                                               H        (CH.sub.3).sub.2 CHCH.sub.2 CH(CH.sub.3)                                                     H        (CH.sub.3).sub.2 CHCH.sub.2                                                    CH(CH.sub.3)  128-131°         56     Br                                                                               H        CH.sub.3 (CH.sub.2).sub.5                                                                    H        CH.sub.3 (CH.sub.2).sub.5                                                                    126-127°         57     Br                                                                               H        CH.sub.3 (CH.sub.2).sub.2 CH(CH.sub.3)                                                       H        CH.sub.3 (CH.sub.2).sub.2                                                      CH(CH.sub.3)  164-165°         58     Br                                                                               H        (CH.sub.3 CH.sub.2).sub.2 CH                                                                 H        (CH.sub.3 CH.sub.2).sub.2                                                                    169°                                                                    (dec.)                  59     Br                                                                               H        ClCHCHCH.sub.2                                                                               H        ClCHCHCH.sub.2                                                                               150°                                                                    (dec.)                  60     Br                                                                               H        Cl.sub.2 CCHCH.sub.2                                                                         H        Cl.sub.2 CCHCH.sub.2                                                                         167°             61     Br                                                                               H                                                                                        ##STR32##    H                                                                                        ##STR33##    172°                                                                    (dec.)                  62     Br                                                                               H        CH.sub.2CH(CH.sub.2).sub.2                                                                   H        CH.sub.2CH(CH.sub.2).sub.2                                                                   145-149°         63     Br                                                                               H        CH.sub.2 CHCH.sub.2                                                                          H        CH.sub.2 CHCH.sub.2                                                                          156-159°         64     Br                                                                               H        (CH.sub.2).sub.3 CHCH.sub.2                                                                  H        (CH.sub.2).sub.3 CHCH.sub.2                                                                  127-130°         65     Br                                                                               H        CH.sub.2 CClCHCl                                                                             H        CH.sub.2 CClCHCl                                                                             140-141.5               66     Br                                                                               H        cycloheptyl   H        cycloheptyl   174°                                                                    (dec.)                  67     Cl                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2 CClCH.sub.2                                                                         CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2 CClCH.sub.2                                                                         1.5096                  68     Br                                                                               H        cyclopentyl   H        cyclopentyl   170°                                                                    (dec.)                  69     Cl                                                                               H        CH.sub.2 CClCH.sub.2                                                                         H        CH.sub.2 CClCH.sub.2                                                                         164°                                                                    (dec.)                  70     Cl                                                                               H        CH.sub.2 CCH  H        CH.sub.2 CCH  145°                                                                    (dec.)                  71     Br                                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)CH(CH.sub.3)                                                   H        CH.sub.3 CH.sub.2 CH(CH.sub.3)CH(                                              CH.sub.3)     135-137°         72     Br                                                                               H        CH.sub.3 (CH.sub.2).sub.3 CH(CH.sub.3)                                                       H        CH.sub.3 (CH.sub.2).sub.3                                                      CH(CH.sub.3)  120-124°         73     Br                                                                               H        CH.sub.3 (CH.sub.2).sub.2 CH(CH.sub.3)CH.sub.2                                               H        CH.sub.3 (CH.sub.2).sub.2                                                      CH(CH.sub.3)CH.sub.2                                                                         111-114                 74     Br                                                                               H                                                                                        ##STR34##    H                                                                                        ##STR35##    160°                                                                    (dec.)                  75     Br                                                                               H                                                                                        ##STR36##    H                                                                                        ##STR37##    66° (dec.)       76     Cl                                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)                                                               170°                                                                    (dec.)                  77     Br                                                                               H        (CH.sub.3).sub.2 CCHCH.sub.2                                                                 H        (CH.sub.3).sub.2 CCHCH.sub.2                                                                 157°                                                                    (dec.)                  78     Br                                                                               H        CH.sub.3 CHCHCH(CH.sub.3)                                                                    H        CH.sub.3 CHCHCH(CH.sub.3)                                                                    138-143°         79     Cl                                                                               H                                                                                        ##STR38##    H                                                                                        ##STR39##    178-180°         80     Cl                                                                               H        CH.sub.3 CHCHCH.sub.2                                                                        H        CH.sub.3 CHCHCH.sub.2                                                                        164-166°         81     Br                                                                               H        CH.sub.3 CClCHCH.sub.2                                                                       H        CH.sub.3 CClCHCH.sub.2                                                                       166-169°         82     Cl                                                                               H        CH.sub.2C(CH.sub.3)CH.sub.2                                                                  H        CH.sub.2C(CH.sub.3)CH.sub.2                                                                  165°                                                                    (dec.)                  83     Cl                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CHCH.sub.2                                                                           CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.2CHCH.sub.2                                                                           1.4926                  84     Cl                                                                               CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                                   CH.sub.3 CH.sub.2 CH.sub.2                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                                   1.4789                  85     Cl                                                                               CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          CH.sub.2CHCH.sub.2                                                                      CH.sub.2CClCH.sub.2                                                                          1.5210                  86     Cl                                                                               H        CH.sub.3      H        CH.sub.3      141-143°         87     Cl                                                                               H        C.sub.2 H.sub.5                                                                              H        C.sub.2 H.sub.5                                                                              195-197°         88     Cl                                                                               H        CH.sub.3 CH.sub.2 CH.sub.2                                                                   H        CH.sub.3 CH.sub.2 CH.sub.2                                                                   173-176°         89     Cl                                                                               H        (CH.sub.3).sub.2 CH                                                                          H        (CH.sub.3).sub.2 CH                                                                          190°                                                                    (dec.)                  90     Cl                                                                               H        CH.sub.3 (CH.sub.2).sub.3                                                                    H        CH.sub.3 (CH.sub.2).sub.3                                                                    142-144°         91     Cl                                                                               H        (CH.sub.3).sub.2 CHCH.sub.2                                                                  H        (CH.sub.3).sub.2 CHCH.sub.2                                                                  165°                                                                    (dec.)                  92     Cl                                                                               H        CH.sub.3 (CH.sub.2).sub.4                                                                    H        CH.sub.3 (CH.sub.2).sub.4                                                                    125-129°         93     Cl                                                                               H        (CH.sub.3).sub.2 CH(CH.sub.2).sub.2                                                          H        (CH.sub.3).sub.2 CH(CH.sub.2).sub                                              .2            119-124°         94     Cl                                                                               H        CH.sub.3 (CH.sub.2).sub.2 CH(CH.sub.3)                                                       H        CH.sub.3 (CH.sub.2).sub.2                                                      CH(CH.sub.3)  160°                                                                    (dec.)                  95     Cl                                                                               H        CH.sub.3 CH.sub.2 CH(CH.sub.3)CH(CH.sub.3)                                                   H        CH.sub.3 CH.sub.2 CH(CH.sub.3)CH(                                              CH.sub.3)     120-125°         96     Cl                                                                               H        CH.sub.3 (CH.sub.2).sub.3 CH(CH.sub.3)                                                       H        CH.sub.3 (CH.sub.2).sub.3                                                      CH(CH.sub.3)  108-111°         __________________________________________________________________________

HERBICIDAL SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Compounds of this invention are tested as herbicides in the following manner.

Pre-emergence Herbicide Screening Test

Using an analytical balance, 20 mg. of the compound to be tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 30 ml. wide-mouth bottle and 3 ml. of acetone containing 1% Tween 20® (polyoxyethylene sorbitan monolaurate) is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml. or less is used to dissolve the compound and then another solvent is used to make the volume up to 3 ml. The 3 ml. of solution is sprayed uniformly on the soil contained in a small flat one day after planting weed seeds in the flat of soil. An atomizer is used to apply the spray using compressed air at a pressure of 5 lb./sq. inch. The rate of application is 8 lb/acre and the spray volume is 143 gallons per acre.

On the day preceeding treatment, the flat which is 7 inches long, 5 inches wide and 2.75 inches deep, is filled to a depth of 2 inches with loamy sand soil. Seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds are covered with soil so that they are planted at a depth of 0.5 inch. Ample seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plants.

The seeds used are foxtail (Setaria spp.)-FT; watergrass (Echinochloa crusgalli)-WG; red oat (Avena sativa)-RO; redroot pigweed (Amaranthus retroflexus)-PW; mustard (Brassica juncea)-MD; curly dock (Rumex crispus)-CD; and hairy crabgrass (Digitaria sanguinalis)-CG.

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 85° F. and watered by sprinkling. Two weeds after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete kill.

Post-emergence Herbicide Screening Test

Seeds of six plant species, including hairy crabgrass (CG), watergrass (WG), red oat (RO), mustard (MD), curly dock (CD) and Pinto beans (Phaseolus vulgaris) (BN), are planted in the flats as described above for pre-emergence screening. The flats are planted in the greenhouse at 70° to 85° F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plants are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 20 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1% Tween 20® (polyoxyethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foilage using an atomizer at an air pressure of 5 lb/sq. inch. The spray concentration is 0.2% and the rate is 8 lb/acre. The spray volume is 476 gallons per acre.

The results of these tests are shown in Table II.

                  TABLE II                                                         ______________________________________                                         HERBICIDAL ACTIVITY - SCREENING RESULTS                                        ______________________________________                                         Per Cent Control at 8 lb/A.                                                    COMPOUND                                                                       NUMBER      CG     FT     WG   RO   PW   MD   CD                               ______________________________________                                         1           90     95     100  30   0    0    0                                2           100    100    100  100  100  100  50                               3           100    99     100  99   98   80   40                               4           80     50     50   40   0    20   20                               5           100    100    100  99   98   100  30                               6           100    99     99   98   100  80   20                               7           100    99     100  98   90   90   20                               8           99     100    99   100  99   90   80                               9           90     90     90   80   20   10   10                               10          100    98     99   98   50   80   30                               11          100    99     99   95   100  60   20                               12          100    100    100  98   100  80   30                               15          90     80     70   0    0    0    0                                16          80     80     70   40   0    0    0                                17          90     90     80   0    0    0    10                               18          20     0      0    0    0    0    0                                19          95     80     90   70   0    0    0                                20          98     98     100  95   80   40   20                               21          90     90     80   70   0    0    0                                23          100    100    100  95   80   20   30                               24          98     100    98   90   80   20   20                               25          100    100    95   90   70   10   10                               31          80     70     70   10   0    0    0                                32          100    90     90   70   0    0    10                               33          100    100    100  90   70   80   20                               34          90     100    95   70   0    0    0                                35          100    100    100  80   100  100  70                               36          100    100    100  80   20   40   0                                37          100    100    100  60   0    0    0                                38          100    100    100  98   100  98   90                               39          100    99     100  100  50   50   50                               40          98     98     100  95   30   40   30                               41          100    100    100  95   70   20   20                               42          100    100    100  95   0    40   30                               43          99     98     100  90   20   50   20                               44          100    100    100  40   70   60   20                               45          100    100    100  20   80   60   0                                47          100    98     100  60   0    10   0                                48          100    100    100  70   0    0    0                                49          80     80     80   60   0    0    0                                50          98     98     100  98   0    20   0                                51          98     98     100  100  0    20   10                               52          98     100    100  80   0    40   0                                53          98     100    100  90   0    50   0                                54          98     100    100  100  80   50   20                               55          100    100    100  20   0    0    0                                56          90     98     100  20   0    0    0                                57          100    100    100  98   0    90   50                               58          100    100    100  100  0    0    0                                59          100    100    100  80   0    0    0                                60          80     90     90   0    0    0    0                                61          95     100    100  90   20   20   10                               62          100    100    100  80   0    20   0                                63          99     100    100  98   60   60   30                               64          100    100    100  70   0    0    0                                65          100    80     80   0    0    0    0                                66          70     80     70   0    0    0    0                                67          100    100    80   0    0    0    0                                68          100    100    100  80   0    0    0                                69          80     80     80   10   0    0    0                                70          70     70     10   0    0    0                                     71          90     80     80   20   0    0    0                                72          90     90     95   40   10   0    0                                73          90     98     95   0    0    0    0                                74          98     100    100  70   20   10   10                               75          90     90     80   20   0    0    0                                76          90     90     80   80   0    0    0                                77          90     90     90   20   0    0    0                                78          100    100    100  98   50   40   30                               79          30     30     10   10   0    0    0                                80          80     80     80   0    0    0    0                                81          90     95     95   0    0    0    0                                82          95     95     95   10   0    0    0                                83          100    100    100  90   0    0    0                                84          98     95     98   60   0    0    0                                85          100    100    100  60   0    0    0                                86          0      0      0    0    0    0    0                                87          0      0      0    0    0    0    0                                88          95     98     98   0    0    0    0                                89          98     98     98   30   50   0    0                                90          98     98     98   50   0    0    0                                91          98     95     95   50   0    0    0                                92          90     80     95   10   0    0    0                                93          90     20     30   0    0    0    0                                94          99     98     95   0    0    0    0                                95          90     70     10   0    0    0    0                                96          99     98     98   10   0    0    0                                ______________________________________                                         Post-emergence                                                                 COMPOUND                                                                       NUMBER      CG     WG      RO   MD    CD   BN                                  ______________________________________                                         1           0      0       0    0     0    0                                   2           90     95      70   100   0    98                                  3           80     80      80   90    0    60                                  4           20     0       0    10    0    20                                  5           90     80      80   90    0    0                                   6           80     70      70   100   0    70                                  7           50     50      40   20    10   20                                  8           80     80      60   90    20   80                                  9           90     70      30   30    0    20                                  10          80     70      50   100   100  80                                  11          50     40      60   80    0    80                                  12          90     80      70   100   20   100                                 15          70     20      10   0     0    0                                   16          70     60      40   10    10   10                                  17          80     60      20   30    10   30                                  18          40     50      10   20    0    0                                   19          80     70      0    0     0    20                                  20          90     80      70   90    20   100                                 21          80     70      60   0     0    0                                   23          100    100     70   90    30   10                                  24          95     90      80   100   10   10                                  25          90     90      80   20    10   30                                  27          80     20      10   0     0    0                                   31          70     50      10   10    10   20                                  32          80     80      70   0     0    0                                   33          80     90      70   80    20   100                                 34          80     80      80   30    10   80                                  35          80     80      80   20    20   100                                 36          80     80      70   80    10   100                                 37          80     100     70   0     0    80                                  38          90     90      50   80    20   80                                  39          80     80      60   10    0    10                                  40          80     100     60   70    20   100                                 41          80     90      70   20    0    80                                  42          90     90      60   20    20   80                                  43          80     80      60   20    20   70                                  44          100    100     60   100   70   30                                  45          100    100     20   100   10   40                                  46          20     10      0    0     0    10                                  47          80     60      20   10    0    0                                   48          100    100     60   50    20   80                                  50          80     70      50   20    10   80                                  51          80     70      50   0     0    80                                  52          80     70      70   80    0    70                                  53          80     70      70   70    0    80                                  54          80     80      70   90    20   100                                 55          70     60      50   0     0    80                                  56          70     70      40   70    0    20                                  57          80     70      70   60    20   80                                  58          50     40      20   0     0    60                                  59          70     60      50   0     0    80                                  60          60     20      0    0     0    0                                   61          100    80      60   80    20   80                                  62          90     80      60   0     0    80                                  63          80     80      60   100   50   100                                 64          40     50      0    80    0    50                                  65          80     50      0    70    0    0                                   66          0      0       0    0     0    0                                   67          100    50      0    80    0    0                                   68          80     60      40   100   80   80                                  69          50     40      0    20    0    10                                  70          30     50      10   20    0    20                                  71          80     80      40   10    0    80                                  72          80     95      70   20    0    80                                  73          70     70      20   20    0    80                                  74          80     95      60   20    0    80                                  75          70     70      0    20    10   20                                  76          60     60      10   20    0    80                                  77          70     70      10   0     0    10                                  78          90     80      70   40    30   90                                  79          0      0       0    0     0    30                                  80          40     0       0    30    0    20                                  81          70     40      0    20    0    20                                  82          80     70      0    0     0    10                                  83          90     90      40   20    0    95                                  84          95     90      0    0     0    50                                  85          90     90      0    80    0    50                                  86          10     0       0    0     0    0                                   87          10     10      0    0     0    0                                   88          80     80      20   0     0    20                                  89          40     60      0    0     0    20                                  90          95     60      0    0     0    0                                   91          80     60      0    0     0    20                                  92          40     0       0    0     0    0                                   93          10     60      0    10    10   10                                  94          70     70      10   10    0    80                                  95          0      0       0    0     0    0                                   96          80     60      0    60    0    10                                  ______________________________________                                    

The compounds of the present invention are used as pre-emergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert carrier, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like, in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. An herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from 0.10 to approximately 50 pounds per acre. The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed, is readily determinable by those skilled in the art.

The phytotoxic compositions of this invention employing an herbicidally effective amount of the compound described herein are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. 

What is claimed is:
 1. A compound in which the formula is ##STR40## in which X is chlorine or bromine; and in which each R₁ and R₂ taken together and R₃ and R₄ taken together is an alkenylene having 4 or 5 carbon atoms, inclusive.
 2. A compound according to claim 1 in which X is chlorine, R₁ and R₂ taken together and R₃ and R₄ taken together are each 2-pentenylene.
 3. A compound according to claim 1 in which X is bromine, R₁ and R₂ taken together and R₃ and R₄ taken together are each 2-pentenylene.
 4. A compound according to claim 1 in which X is chlorine, R₁ and R₂ taken together and R₃ and R₄ taken together are each 2-butenylene.
 5. A compound having the formula ##STR41## R₁ and R₂ taken together are β-oxydiethylene and R₃ and R₄ taken together are β-oxydiethylene. 